US20100220018A1 - Ice and snow accretion-preventive antenna, electric wire, and insulator having water-repellent, oil-repellent, and antifouling surface and method for manufacturing the same - Google Patents

Ice and snow accretion-preventive antenna, electric wire, and insulator having water-repellent, oil-repellent, and antifouling surface and method for manufacturing the same Download PDF

Info

Publication number
US20100220018A1
US20100220018A1 US12/600,144 US60014408A US2010220018A1 US 20100220018 A1 US20100220018 A1 US 20100220018A1 US 60014408 A US60014408 A US 60014408A US 2010220018 A1 US2010220018 A1 US 2010220018A1
Authority
US
United States
Prior art keywords
repellent
ice
roughness
antenna
preventive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US12/600,144
Other versions
US8872709B2 (en
Inventor
Kazufumi Ogawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Empire Technology Development LLC
Original Assignee
Kazufumi Ogawa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kazufumi Ogawa filed Critical Kazufumi Ogawa
Publication of US20100220018A1 publication Critical patent/US20100220018A1/en
Assigned to EMPIRE TECHNOLOGY DEVELOPMENT LLC reassignment EMPIRE TECHNOLOGY DEVELOPMENT LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OGAWA, KAZUFUMI
Assigned to EMPIRE TECHNOLOGY DEVELOPMENT LLC reassignment EMPIRE TECHNOLOGY DEVELOPMENT LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OGAWA, KAZUFUMI
Application granted granted Critical
Publication of US8872709B2 publication Critical patent/US8872709B2/en
Assigned to CRESTLINE DIRECT FINANCE, L.P. reassignment CRESTLINE DIRECT FINANCE, L.P. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EMPIRE TECHNOLOGY DEVELOPMENT LLC
Assigned to EMPIRE TECHNOLOGY DEVELOPMENT LLC reassignment EMPIRE TECHNOLOGY DEVELOPMENT LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: CRESTLINE DIRECT FINANCE, L.P.
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/02—Arrangements for de-icing; Arrangements for drying-out ; Arrangements for cooling; Arrangements for preventing corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers

Definitions

  • the present invention relates to an ice and snow accretion-preventive antenna, electric wire, and insulator having a very low surface energy to such an extent that the surface thereof repels silicone oil.
  • the present invention relates to a method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator.
  • a surface which has roughness with a size of about 10 micrometers and in which the surfaces of the roughness are coated with a coating film made of a fatty acid exhibits ultra water-repellency, such that a water-repellency angle for a water droplet of about 140 degrees is achieved, as observed with a lotus leaf.
  • the present invention is made by imitating and improving upon this principle.
  • antennas, electric wires, and insulators serving as lifelines are essential equipment for maintaining life in heavy snowfall areas.
  • breakage of antennas and insulators and accidents due to breakage of electric wires caused by ice and snow accretion constantly occur. Consequently, some antennas and the like are coated with a fluorine coating material to prevent ice and snow accretion.
  • the surface energy of a fluorocarbon resin is at least about 15 mN/m, which is not sufficient in terms of an effect for ice and snow accretion.
  • the technique can be used for, for example, preventing ice and snow accretion on various types of weather observation instruments such as rain gauges, preventing ice accretion on a dispensing portion of a liquid nitrogen tank or a liquid oxygen tank, and preventing ice accretion on an external fuel tank of a space shuttle. Accordingly, a significant effect of preventing accidents caused by ice accretion can be achieved.
  • a first invention provided as means for solving the above problem is an ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface thereof is compositely fabricated to have large roughness and small roughness, and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film.
  • a second invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to the first invention, wherein the large roughness has a size in the range of 500 to 10 ⁇ m, and the small roughness has a size of less than 10 ⁇ m and 10 nm or more.
  • a third invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to the first invention, wherein the area of a convex portion of the large roughness is smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is smaller than the depth of a concave portion thereof.
  • a fourth invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to any one of the first to third inventions, wherein the water-repellent, oil-repellent, and antifouling thin film is covalently bonded to the surfaces of the roughness of both types.
  • a fifth invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to the fourth invention, wherein the water-repellent, oil-repellent, and antifouling thin film contains a —CF 3 group.
  • a sixth invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to any one of the first to fifth inventions, wherein the water-repellent, oil-repellent, and antifouling thin film is a monomolecular film.
  • a seventh invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to any one of the first to sixth inventions, wherein a critical surface energy of the surface is 2 mN/m or less.
  • An eighth invention is a method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator including at least the steps of processing a surface by blasting or dimpling, performing chemical etching or electrolytic etching, and forming a water-repellent, oil-repellent, and antifouling thin film.
  • a ninth invention is the method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to the eighth invention, wherein the step of forming the water-repellent, oil-repellent, and antifouling thin film includes a step of forming the water-repellent, oil-repellent, and antifouling coating film using a reaction solution prepared by mixing an alkoxysilane compound having a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a nonaqueous organic solvent, a reaction solution prepared by mixing a chlorosilane compound having a fluorocarbon group and a trichlorosilyl group with a nonaqueous organic solvent, or a reaction solution prepared by mixing an isocyanate compound having a fluorocarbon group and an isocyanate group with a nonaqueous organic solvent.
  • a tenth invention is the method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to the eighth or ninth invention, wherein the step of forming the water-repellent, oil-repellent, and antifouling thin film includes a step of removing excess reaction solution by washing, the step being performed after contact.
  • An eleventh invention is the method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to the ninth or tenth invention, wherein at least one selected from ketimine compounds, organic acids, metal oxides, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a cocatalyst is used to be mixed with the silanol condensation catalyst.
  • the present invention provides an ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface thereof is compositely fabricated to have large roughness and small roughness and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film, the ice and snow accretion-preventive antenna, electric wire, and insulator being produced by at least a step of processing the surface by blasting or dimpling, performing chemical etching or electrolytic etching, and forming the water-repellent, oil-repellent, and antifouling thin film.
  • the large roughness preferably have a size in the range of 500 to 10 ⁇ m, and the small roughness preferably have a size of less than 10 ⁇ m and 10 nm or more. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • the area of a convex portion of the large roughness is preferably smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is preferably smaller than the depth of a concave portion thereof. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • the water-repellent, oil-repellent, and antifouling thin film is covalently bonded to the surfaces of the roughness of both types. This is advantageous in that the durability of water-repellent, oil-repellent, and antifouling performance is improved.
  • the water-repellent, oil-repellent, and antifouling thin film preferably contains a —CF 3 group. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • the water-repellent, oil-repellent, and antifouling thin film is preferably a monomolecular film. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • the step of forming a water-repellent, oil-repellent, and antifouling thin film preferably includes a step of forming the water-repellent, oil-repellent, and antifouling coating film using a reaction solution prepared by mixing an alkoxysilane compound having a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a nonaqueous organic solvent, a reaction solution prepared by mixing a chlorosilane compound having a fluorocarbon group and a trichlorosilyl group with a nonaqueous organic solvent, or a reaction solution prepared by mixing an isocyanate compound having a fluorocarbon group and an isocyanate group with a nonaqueous organic solvent.
  • This is advantageous in that the manufacturing time of the ice and snow accretion-preventive antenna, electric wire, and insulator can be reduced.
  • the step of forming a water-repellent, oil-repellent, and antifouling thin film preferably includes a step of removing excess reaction solution by washing, the step being performed after contact. This is advantageous in that the roughness of the base material is not impaired at all.
  • At least one selected from ketimine compounds, organic acids, metal oxides, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a cocatalyst is preferably used to be mixed with a silanol condensation catalyst. This is advantageous in that the manufacturing time of the ice and snow accretion-preventive antenna, electric wire, and insulator can be reduced.
  • FIG. 1 is a schematic cross-sectional view showing a state in which large roughness 2 having a roughness in the range of 100 to 200 ⁇ m are formed on a surface of aluminum in Example 1 of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a state in which the large roughness 2 having a roughness in the range of 100 to 200 ⁇ m are formed on the surface of aluminum, and small roughness 2 having a roughness in the range of 2 to 0.5 ⁇ m are then compositely formed by further etching the surface with a phosphoric acid etchant in Example 1 of the present invention.
  • FIG. 3 includes schematic cross-sectional views in which portion A surrounded by the circle in FIG. 2 is enlarged to the molecular level.
  • A is a schematic cross-sectional view of the portion near the surface before a monomolecular film is formed
  • (B) is a schematic cross-sectional view of the portion near the surface after the monomolecular film is formed.
  • FIG. 4 is a schematic cross-sectional view showing a state in which, after the roughening treatment, a water-repellent, oil-repellent, and antifouling monomolecular film is formed on the surface.
  • FIG. 5 includes SEM images of a surface of an ice and snow accretion-preventive antenna as a trial product whose surface is compositely fabricated to have large roughness and small roughness and is coated with a water-repellent, oil-repellent, and antifouling thin film.
  • the scale bar of ⁇ 500 represents 50 ⁇ m
  • the scale bar of ⁇ 5,000 represents 5 ⁇ m
  • the scale bar of ⁇ 10,000 represents 1 ⁇ m
  • the scale bar of ⁇ 20,000 represents 1 ⁇ m.
  • FIG. 6 is a cross-sectional photograph of a droplet when a silicone oil is dripped on the surface of the ice and snow accretion-preventive antenna shown in FIG. 5 .
  • the present invention provides an ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface thereof is compositely fabricated to have large roughness and small roughness and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film, the antenna, electric wire, and insulator being manufactured by at least a step of processing the surface by blasting or dimpling, performing chemical etching or electrolytic etching, and forming the water-repellent, oil-repellent, and antifouling thin film.
  • the present invention has a function for realizing a surface for which the angle of contact for a water droplet is 150 degrees or more, and for which the angle of contact for even a droplet of a silicone oil having a surface energy of about 20 mN/m is about 120 degrees.
  • the present invention can be used for, for example, preventing ice and snow accretion on various types of weather observation instruments such as rain gauges, preventing ice accretion on a dispensing portion of a liquid nitrogen tank or a liquid oxygen tank, and preventing ice accretion on an external fuel tank of a space shuttle.
  • any material can be used as the ice and snow accretion-preventive antenna and electric wire related to the present invention as long as the material is a metal that can undergo electrolytic etching (e.g., aluminum and alloys thereof, copper and alloys thereof, and iron and alloys thereof).
  • electrolytic etching e.g., aluminum and alloys thereof, copper and alloys thereof, and iron and alloys thereof.
  • a description will now be made using, as a typical example, a parabolic antenna made of an aluminum alloy.
  • a surface of the ceramic product is processed by blasting to form roughness, and a water-repellent treatment can then be performed in the same manner.
  • a chemical agent having a fluorocarbon group ( ⁇ CF 3 ) at one end thereof and an alkoxysilyl group at another end thereof, for example, 99 weight percent of a chemical agent represented by CF 3 (CF 2 ) 7 (CH 2 ) 2 Si(OCH 3 ) 3 and 1 weight percent of a silanol condensation catalyst, for example, dibutyltin diacetylacetonate were weighed.
  • the chemical agent and the silanol condensation catalyst were dissolved in a silicone solvent, for example, a hexamethyldisiloxane solvent in a concentration of about 1 weight percent (a preferable concentration of a chemisorption agent was in the range of about 0.5% to 3%) to prepare a reaction solution.
  • an aluminum plate 1 used as a concave portion of a parabolic antenna and having a thickness of about 2 mm was prepared and sufficiently washed. A blasting process was then performed over the entire surface of the aluminum plate 1 using an emery powder of #30 to form large roughness 2 having a roughness in the range of 100 to 200 ⁇ m ( FIG. 1 ).
  • the surface was etched using a phosphoric acid etchant to form small roughness 3 having a roughness in the range of 2 to 0.5 ⁇ m ( FIG. 2 ).
  • a chemisorbed monomolecular film 5 containing a fluorocarbon group represented by formula (Chemical Formula 1) below was formed over the entire surface of the aluminum plate 1 ′ by being chemically bonded to the surface to have a thickness of about 1 nm ( FIG. 3(B) ).
  • the surface roughness in this case was examined. According to the results, it was found that the area of a convex portion of the large roughness was smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness was smaller than the depth of a concave portion thereof.
  • FIG. 5 shows SEM observation images of the surface of a substrate under this condition.
  • FIG. 6 shows a cross-sectional photograph showing an oil-repellent state of a droplet of the silicone oil (having a surface energy of 19.7 mN/m).
  • Example 1 CF 3 (CF 2 ) 7 (CH 2 ) 2 Si(OCH 3 ) 3 which is a fluorocarbon chemisorption agent was used as a chemical agent for forming the oil-repellent monomolecular film.
  • substances represented by (1) to (12) below could also be used.
  • a thiol-terminated or triazinethiol-terminated chemical agent for example, CF 3 (CF 2 ) 7 (CH 2 ) 2 SH could be used.
  • an SH group was bonded to gold, thus producing a similar water-repellent and oil-repellent film.
  • carboxylic acid metal salts carboxylate metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanates, and titanate chelates
  • Example 1 in the case where a silanol condensation catalyst was not used, substances represented by (41) to (52) below could be used.
  • the solvent of the reaction solution for forming a film in both the case where the chemisorption agent was an alkoxysilane compound and the case where the chemisorption agent was a chlorosilane compound, organochlorine solvents, hydrocarbon solvents, fluorocarbon solvents, and silicone solvents, all of which did not contain water, and mixtures thereof could be used.
  • the boiling point of the solvent was preferably in the range of about 50° C. to 250° C.
  • solvents that can be used include nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonanes, decanes, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, and dimethylformamide.
  • adsorbent was an alkoxysilane compound and an organic coating film was formed by evaporating a solvent
  • alcohol solvents such as methanol, ethanol, and propanols, and mixtures thereof could be used.
  • fluorocarbon solvents examples include chlorofluorocarbon solvents, Fluorinert (a product available from 3M), and Aflude (a product available from Asahi Glass Co., Ltd.). These may be used alone or in combination of two or more solvents that can be sufficiently mixed with each other. Furthermore, an organochlorine solvent such as chloroform may be added to the solvent.
  • the processing time could be reduced to about 1 ⁇ 2 to 2 ⁇ 3.
  • the silanol condensation catalyst was mixed with a ketimine compound, an organic acid, a metal oxide such as TiO 2 , an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound (these compounds could be used at a mixing ratio in the range of 1:9 to 9:1, but a ratio of about 1:1 was generally preferable) for use, the processing time could be further reduced several-folds, and thus, the film formation time could be reduced to a fraction of the film formation time when these compounds are not used.
  • ketimine compounds that can be used here include, but are not particularly limited to, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, and 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene.
  • organic acids examples include, but are also not particularly limited to, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid. These organic acids achieved substantially the same effects.

Abstract

A representative embodiment prevents breakage of antennas and accidents due to breakage of electric wires caused by ice and snow accretion by realizing a surface with a surface energy of 2 mN/m or less and providing an antenna and electric wire having an extremely great effect of preventing ice and snow accretion at midwinter.
Another representative embodiment provides an ice and snow accretion-preventive antenna and electric wire wherein a surface thereof is compositely fabricated to have large roughness and small roughness, and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film.

Description

    TECHNICAL FIELD
  • The present invention relates to an ice and snow accretion-preventive antenna, electric wire, and insulator having a very low surface energy to such an extent that the surface thereof repels silicone oil. In addition, the present invention relates to a method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator.
    • BACKGROUND ART
  • In general, it is known that a surface which has roughness with a size of about 10 micrometers and in which the surfaces of the roughness are coated with a coating film made of a fatty acid exhibits ultra water-repellency, such that a water-repellency angle for a water droplet of about 140 degrees is achieved, as observed with a lotus leaf. The present invention is made by imitating and improving upon this principle.
    • DISCLOSURE OF INVENTION Problem to be Solved by the Invention
  • Nowadays, antennas, electric wires, and insulators serving as lifelines are essential equipment for maintaining life in heavy snowfall areas. However, under the present situation, at midwinter, breakage of antennas and insulators and accidents due to breakage of electric wires caused by ice and snow accretion constantly occur. Consequently, some antennas and the like are coated with a fluorine coating material to prevent ice and snow accretion. However, the surface energy of a fluorocarbon resin is at least about 15 mN/m, which is not sufficient in terms of an effect for ice and snow accretion.
  • In view of the above-described present situation, it is an object of the present invention to prevent breakage of antennas and insulators and accidents due to breakage of electric wires caused by ice and snow accretion by realizing a surface with a surface energy of 2 mN/m or less and providing an antenna, electric wire, and insulator having an extremely great effect of preventing ice and snow accretion at midwinter.
  • In the case where the above physical property value can be realized, the technique can be used for, for example, preventing ice and snow accretion on various types of weather observation instruments such as rain gauges, preventing ice accretion on a dispensing portion of a liquid nitrogen tank or a liquid oxygen tank, and preventing ice accretion on an external fuel tank of a space shuttle. Accordingly, a significant effect of preventing accidents caused by ice accretion can be achieved.
    • Means for Solving the Problems
  • A first invention provided as means for solving the above problem is an ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface thereof is compositely fabricated to have large roughness and small roughness, and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film.
  • A second invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to the first invention, wherein the large roughness has a size in the range of 500 to 10 μm, and the small roughness has a size of less than 10 μm and 10 nm or more.
  • A third invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to the first invention, wherein the area of a convex portion of the large roughness is smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is smaller than the depth of a concave portion thereof.
  • A fourth invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to any one of the first to third inventions, wherein the water-repellent, oil-repellent, and antifouling thin film is covalently bonded to the surfaces of the roughness of both types.
  • A fifth invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to the fourth invention, wherein the water-repellent, oil-repellent, and antifouling thin film contains a —CF3 group.
  • A sixth invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to any one of the first to fifth inventions, wherein the water-repellent, oil-repellent, and antifouling thin film is a monomolecular film.
  • A seventh invention is the ice and snow accretion-preventive antenna, electric wire, and insulator according to any one of the first to sixth inventions, wherein a critical surface energy of the surface is 2 mN/m or less.
  • An eighth invention is a method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator including at least the steps of processing a surface by blasting or dimpling, performing chemical etching or electrolytic etching, and forming a water-repellent, oil-repellent, and antifouling thin film.
  • A ninth invention is the method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to the eighth invention, wherein the step of forming the water-repellent, oil-repellent, and antifouling thin film includes a step of forming the water-repellent, oil-repellent, and antifouling coating film using a reaction solution prepared by mixing an alkoxysilane compound having a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a nonaqueous organic solvent, a reaction solution prepared by mixing a chlorosilane compound having a fluorocarbon group and a trichlorosilyl group with a nonaqueous organic solvent, or a reaction solution prepared by mixing an isocyanate compound having a fluorocarbon group and an isocyanate group with a nonaqueous organic solvent.
  • A tenth invention is the method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to the eighth or ninth invention, wherein the step of forming the water-repellent, oil-repellent, and antifouling thin film includes a step of removing excess reaction solution by washing, the step being performed after contact.
  • An eleventh invention is the method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to the ninth or tenth invention, wherein at least one selected from ketimine compounds, organic acids, metal oxides, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a cocatalyst is used to be mixed with the silanol condensation catalyst.
  • More specifically, the present invention provides an ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface thereof is compositely fabricated to have large roughness and small roughness and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film, the ice and snow accretion-preventive antenna, electric wire, and insulator being produced by at least a step of processing the surface by blasting or dimpling, performing chemical etching or electrolytic etching, and forming the water-repellent, oil-repellent, and antifouling thin film.
  • Here, the large roughness preferably have a size in the range of 500 to 10 μm, and the small roughness preferably have a size of less than 10 μm and 10 nm or more. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • In addition, the area of a convex portion of the large roughness is preferably smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is preferably smaller than the depth of a concave portion thereof. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • In addition, preferably, the water-repellent, oil-repellent, and antifouling thin film is covalently bonded to the surfaces of the roughness of both types. This is advantageous in that the durability of water-repellent, oil-repellent, and antifouling performance is improved.
  • Furthermore, the water-repellent, oil-repellent, and antifouling thin film preferably contains a —CF3 group. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • In addition, the water-repellent, oil-repellent, and antifouling thin film is preferably a monomolecular film. This is advantageous in that the critical surface energy can be made to be 2 mN/m or less.
  • In addition, in this case, the step of forming a water-repellent, oil-repellent, and antifouling thin film preferably includes a step of forming the water-repellent, oil-repellent, and antifouling coating film using a reaction solution prepared by mixing an alkoxysilane compound having a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a nonaqueous organic solvent, a reaction solution prepared by mixing a chlorosilane compound having a fluorocarbon group and a trichlorosilyl group with a nonaqueous organic solvent, or a reaction solution prepared by mixing an isocyanate compound having a fluorocarbon group and an isocyanate group with a nonaqueous organic solvent. This is advantageous in that the manufacturing time of the ice and snow accretion-preventive antenna, electric wire, and insulator can be reduced.
  • In addition, the step of forming a water-repellent, oil-repellent, and antifouling thin film preferably includes a step of removing excess reaction solution by washing, the step being performed after contact. This is advantageous in that the roughness of the base material is not impaired at all.
  • Furthermore, at least one selected from ketimine compounds, organic acids, metal oxides, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a cocatalyst is preferably used to be mixed with a silanol condensation catalyst. This is advantageous in that the manufacturing time of the ice and snow accretion-preventive antenna, electric wire, and insulator can be reduced.
    • Advantages
  • By providing an antenna, electric wire, and insulator having an extremely high effect of preventing ice and snow accretion at midwinter, breakage of antennas and accidents due to breakage of electric wires and insulators caused by ice and snow accretion can be advantageously prevented.
    • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a schematic cross-sectional view showing a state in which large roughness 2 having a roughness in the range of 100 to 200 μm are formed on a surface of aluminum in Example 1 of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a state in which the large roughness 2 having a roughness in the range of 100 to 200 μm are formed on the surface of aluminum, and small roughness 2 having a roughness in the range of 2 to 0.5 μm are then compositely formed by further etching the surface with a phosphoric acid etchant in Example 1 of the present invention.
  • FIG. 3 includes schematic cross-sectional views in which portion A surrounded by the circle in FIG. 2 is enlarged to the molecular level. (A) is a schematic cross-sectional view of the portion near the surface before a monomolecular film is formed, and (B) is a schematic cross-sectional view of the portion near the surface after the monomolecular film is formed.
  • FIG. 4 is a schematic cross-sectional view showing a state in which, after the roughening treatment, a water-repellent, oil-repellent, and antifouling monomolecular film is formed on the surface.
  • FIG. 5 includes SEM images of a surface of an ice and snow accretion-preventive antenna as a trial product whose surface is compositely fabricated to have large roughness and small roughness and is coated with a water-repellent, oil-repellent, and antifouling thin film. Note that the scale bar of ×500 represents 50 μm, the scale bar of ×5,000 represents 5 μm, the scale bar of ×10,000 represents 1 μm, and the scale bar of ×20,000 represents 1 μm.
  • FIG. 6 is a cross-sectional photograph of a droplet when a silicone oil is dripped on the surface of the ice and snow accretion-preventive antenna shown in FIG. 5.
    •  BEST MODE FOR CARRYING OUT THE INVENTION
  • The present invention provides an ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface thereof is compositely fabricated to have large roughness and small roughness and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film, the antenna, electric wire, and insulator being manufactured by at least a step of processing the surface by blasting or dimpling, performing chemical etching or electrolytic etching, and forming the water-repellent, oil-repellent, and antifouling thin film.
  • Accordingly, the present invention has a function for realizing a surface for which the angle of contact for a water droplet is 150 degrees or more, and for which the angle of contact for even a droplet of a silicone oil having a surface energy of about 20 mN/m is about 120 degrees.
  • Details of the present invention will now be described using Examples, but the present invention is not limited to the Examples. In addition to an antenna, an electric wire, and an insulator, the present invention can be used for, for example, preventing ice and snow accretion on various types of weather observation instruments such as rain gauges, preventing ice accretion on a dispensing portion of a liquid nitrogen tank or a liquid oxygen tank, and preventing ice accretion on an external fuel tank of a space shuttle.
  • Any material can be used as the ice and snow accretion-preventive antenna and electric wire related to the present invention as long as the material is a metal that can undergo electrolytic etching (e.g., aluminum and alloys thereof, copper and alloys thereof, and iron and alloys thereof). A description will now be made using, as a typical example, a parabolic antenna made of an aluminum alloy. On the other hand, for a ceramic product such as an insulator, a surface of the ceramic product is processed by blasting to form roughness, and a water-repellent treatment can then be performed in the same manner.
    • EXAMPLE 1
  • A chemical agent having a fluorocarbon group (−CF3) at one end thereof and an alkoxysilyl group at another end thereof, for example, 99 weight percent of a chemical agent represented by CF3(CF2)7(CH2)2Si(OCH3)3 and 1 weight percent of a silanol condensation catalyst, for example, dibutyltin diacetylacetonate were weighed. The chemical agent and the silanol condensation catalyst were dissolved in a silicone solvent, for example, a hexamethyldisiloxane solvent in a concentration of about 1 weight percent (a preferable concentration of a chemisorption agent was in the range of about 0.5% to 3%) to prepare a reaction solution.
  • On the other hand, an aluminum plate 1 used as a concave portion of a parabolic antenna and having a thickness of about 2 mm was prepared and sufficiently washed. A blasting process was then performed over the entire surface of the aluminum plate 1 using an emery powder of #30 to form large roughness 2 having a roughness in the range of 100 to 200 μm (FIG. 1).
  • Furthermore, the surface was etched using a phosphoric acid etchant to form small roughness 3 having a roughness in the range of 2 to 0.5 μm (FIG. 2).
  • Subsequently, the above aluminum plate 1′ whose surface was compositely fabricated to have large roughness and small roughness was immersed in the reaction solution, and a reaction was performed for about one hour under stirring in air (relative humidity of 45%). A large number of hydroxyl groups 4 were contained on the surface the aluminum plate 1′ (FIG. 3(A)). Accordingly, in this step, a —Si(OCH3) group of the chemisorption agent and the hydroxyl group 2 were subjected to a dealcoholization reaction (demethanol (deCH3OH) in this case) in the presence of the silanol condensation catalyst. Consequently, a chemisorbed monomolecular film 5 containing a fluorocarbon group represented by formula (Chemical Formula 1) below was formed over the entire surface of the aluminum plate 1′ by being chemically bonded to the surface to have a thickness of about 1 nm (FIG. 3(B)).
  • Subsequently, excess unreacted adsorption solution was removed by washing with a chlorinated solvent such as chloroform. Accordingly, an aluminum plate 1″ whose surface was compositely fabricated to have large roughness and small roughness, in which the surface of each of the roughness was coated with the water-repellent, oil-repellent, and antifouling monomolecular film 5, and which had excellent water-repellent and oil-repellent properties could be manufactured (FIG. 4).
  • Here, even when the step of removing excess unreacted adsorption solution by washing was omitted, and the aluminum plate was taken out from the solution without further treatment to vaporize the unreacted adsorption solution, an aluminum plate which had excellent water-repellent and oil-repellent properties and in which no problems occurred at a practical level could be produced, though the performance was somewhat degraded and a monomolecular film could not be obtained.
  • Figure US20100220018A1-20100902-C00001
  • Here, the same experiment was repeated while the condition for the surface roughening was varied. According to the results, it was found that when the large roughness had a size in the range of 500 to 10 μm and the small roughness had a size of less than 10 μm and 10 nm or more, a critical surface energy could be made to be 2 mN/m or less.
  • In addition, the surface roughness in this case was examined. According to the results, it was found that the area of a convex portion of the large roughness was smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness was smaller than the depth of a concave portion thereof.
  • Furthermore, when electrolytic etching was performed instead of chemical etching, the performance could be further improved, and 1 mN/m or less could be easily realized.
  • In particular, when the surface roughness was the values shown in Table 1, an apparent critical surface energy was 1 or less. In this case, the angle of contact for a liquid droplet could be controlled to be 117.6 degrees even when a silicone oil having a surface energy of 19.7 mN/m was used. FIG. 5 shows SEM observation images of the surface of a substrate under this condition. In addition, FIG. 6 shows a cross-sectional photograph showing an oil-repellent state of a droplet of the silicone oil (having a surface energy of 19.7 mN/m).
  • TABLE 1
    Measurement results of the roughness (μm)
    Maximum Average
    Roughness height height Interval
    9.09 51.5 34.5 139
  • In Example 1, CF3(CF2)7(CH2)2Si(OCH3)3 which is a fluorocarbon chemisorption agent was used as a chemical agent for forming the oil-repellent monomolecular film. In addition to the above chemical agent, substances represented by (1) to (12) below could also be used.
    • (1) CF3CH2O(CH2)15Si(OCH3)3
    • (2) CF3(CH2)3Si(CH3)2(CH2)15Si(OCH3)3
    • (3) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9Si(OCH3)3
    • (4) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9Si(OCH3)3
    • (5) CF3COO(CH2)15Si(OCH3)3
    • (6) CF3(CF2)5(CH2)2Si(OCH3)3
    • (7) CF3CH2O(CH2)15Si(OC2H5)3
    • (8) CF3(CH2)3Si(CH3)2(CH2)15Si(OC2H5)3
    • (9) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9Si(OC2H5)3
    • (10) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9Si(OC2H5)3
    • (11) CF3COO(CH2)15Si(OC2H5)3
    • (12) CF3(CF2)5(CH2)2Si(OC2H5)3
  • Here, when the base material was made of gold, a thiol-terminated or triazinethiol-terminated chemical agent, for example, CF3(CF2)7(CH2)2SH could be used. In this case, an SH group was bonded to gold, thus producing a similar water-repellent and oil-repellent film.
  • Furthermore, in Examples 1 and 2, as the silanol condensation catalyst, carboxylic acid metal salts, carboxylate metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanates, and titanate chelates can be used. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, stannous dioctoate, lead naphthenate, cobalt naphthenate, iron 2-ethylhexenoate, dioctyltin bisoctyl thioglycolate, dioctyltin maleate, dibutyltin maleate polymers, dimethyltin mercaptopropionate polymers, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate, tetrabutyl titanate, tetranonyl titanate, and bis(acetylacetonyl)dipropyl titanate could be used.
  • In Example 1, in the case where a silanol condensation catalyst was not used, substances represented by (41) to (52) below could be used.
    • (41) CF3CH2O(CH2)15SiCl3
    • (42) CF3(CH2)3Si(CH3)2(CH2)15SiCl3
    • (43) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9SiCl3
    • (44) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9SiCl3
    • (45) CF3COO(CH2)15SiCl3
    • (46) CF3(CF2)5(CH2)2Si(NCO)3
    • (47) CF3CH2O(CH2)15Si(NCO)3
    • (48) CF3(CH2)3Si(CH3)2 (CH2)15Si(NCO)3
    • (49) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9Si(NCO)3
    • (50) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9Si(NCO)3
    • (51) CF3COO(CH2)15Si(NCO)3
    • (52) CF3(CF2)5(CH2)2Si(NCO)3
  • Furthermore, as the solvent of the reaction solution for forming a film, in both the case where the chemisorption agent was an alkoxysilane compound and the case where the chemisorption agent was a chlorosilane compound, organochlorine solvents, hydrocarbon solvents, fluorocarbon solvents, and silicone solvents, all of which did not contain water, and mixtures thereof could be used. When the particle concentration was increased by evaporating the solvent without performing washing, the boiling point of the solvent was preferably in the range of about 50° C. to 250° C.
  • In the case of a chlorosilane compound, specific examples of the solvents that can be used include nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonanes, decanes, kerosene, dimethyl silicone, phenyl silicone, alkyl-modified silicone, polyether silicone, and dimethylformamide.
  • Furthermore, when the adsorbent was an alkoxysilane compound and an organic coating film was formed by evaporating a solvent, in addition to the above solvents, alcohol solvents such as methanol, ethanol, and propanols, and mixtures thereof could be used.
  • Examples of the fluorocarbon solvents include chlorofluorocarbon solvents, Fluorinert (a product available from 3M), and Aflude (a product available from Asahi Glass Co., Ltd.). These may be used alone or in combination of two or more solvents that can be sufficiently mixed with each other. Furthermore, an organochlorine solvent such as chloroform may be added to the solvent.
  • On the other hand, instead of the above-described silanol condensation catalyst, when a ketimine compound, an organic acid, a metal oxide such as TiO2, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound was used at the same concentration, the processing time could be reduced to about ½ to ⅔.
  • Furthermore, when the silanol condensation catalyst was mixed with a ketimine compound, an organic acid, a metal oxide such as TiO2, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound (these compounds could be used at a mixing ratio in the range of 1:9 to 9:1, but a ratio of about 1:1 was generally preferable) for use, the processing time could be further reduced several-folds, and thus, the film formation time could be reduced to a fraction of the film formation time when these compounds are not used.
  • For example, when dibutyltin oxide which is a silanol catalyst was replaced with H3, which is a ketimine compound manufactured by Japan Epoxy Resins Co., Ltd., and other conditions were the same, substantially the same results were obtained except that the reaction time could be reduced to about one hour.
  • Furthermore, when the silanol catalyst was replaced with a mixture (mixing ratio: 1:1) of H3, which is a ketimine compound manufactured by Japan Epoxy Resins Co., Ltd., and dibutyltin bisacetylacetonate which is a silanol catalyst and other conditions were the same, substantially the same results were obtained except that the reaction time could be reduced to about 20 minutes.
  • Accordingly, these results showed that the activities of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds were higher than the activities of the silanol condensation catalyst.
  • Furthermore, it was confirmed that when one of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds was mixed with the silanol condensation catalyst for use, the activity was further increased.
  • Examples of the ketimine compounds that can be used here include, but are not particularly limited to, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, and 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene.
  • Examples of the organic acids that can be used include, but are also not particularly limited to, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid. These organic acids achieved substantially the same effects.
    • REFERENCE NUMERALS
    • 1 aluminum plate
    • 1′ aluminum plate whose surface is compositely fabricated to have large roughness and small roughness
    • 1″ aluminum plate whose surface is compositely fabricated to have large roughness and small roughness and on which a water-repellent, oil-repellent, and antifouling monomolecular film is further provided
    • 2 large roughness
    • 3 small roughness
    • 4 hydroxyl group
    • 5 water-repellent, oil-repellent, and antifouling monomolecular film

Claims (13)

1. An ice and snow accretion-preventive antenna, electric wire, and insulator wherein a surface of a base material itself is directly compositely fabricated to have large roughness and small roughness, and the surface of each of the roughness is coated with a water-repellent, oil-repellent, and antifouling thin film.
2. The ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 1, wherein the large roughness has a size in the range of 500 to 10 μm, and the small roughness has a size of less than 10 μm and 10 nm or more.
3. The ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 1, wherein the area of a convex portion of the large roughness is smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is smaller than the depth of a concave portion thereof.
4. The ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 1, wherein the water-repellent, oil-repellent, and antifouling thin film is covalently bonded to the surfaces of the roughness of both types.
5. The ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 4, wherein the water-repellent, oil-repellent, and antifouling thin film contains a —CF3 group.
6. The ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 1, wherein the water-repellent, oil-repellent, and antifouling thin film is a monomolecular film.
7. The ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 1, wherein a critical surface energy of the surface is 2 mN/m or less.
8. A method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator comprising at least the steps of processing a surface of a base material itself by blasting or dimpling, performing chemical etching or electrolytic etching, and forming a water-repellent, oil-repellent, and antifouling thin film.
9. The method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 8, wherein the step of forming the water-repellent, oil-repellent, and antifouling thin film includes a step of forming the water-repellent, oil-repellent, and antifouling coating film using a reaction solution prepared by mixing an alkoxysilane compound having a fluorocarbon group and an alkoxysilyl group, a silanol condensation catalyst, and a nonaqueous organic solvent, a reaction solution prepared by mixing a chlorosilane compound having a fluorocarbon group and a trichlorosilyl group with a nonaqueous organic solvent, or a reaction solution prepared by mixing an isocyanate compound having a fluorocarbon group and an isocyanate group with a nonaqueous organic solvent.
10. The method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 8, wherein the step of forming the water-repellent, oil-repellent, and antifouling thin film includes a step of removing excess reaction solution by washing, the step being performed after contact.
11. The method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator according to claim 9, wherein at least one selected from ketimine compounds, organic acids, metal oxides, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds as a cocatalyst is used to be mixed with the silanol condensation catalyst.
12. An ice and snow accretion-preventive antenna, electric wire, and insulator comprising:
a base material of which surface is directly compositely fabricated to have large roughness having a size in the range of 500 to 10 μm and small roughness having a size of less than 10 μm and 10 nm or more, and
an water-repellent, oil-repellent, and antifouling monomolecular film covering the large roughness and the small roughness and containing —CF3 group,
wherein the area of a convex portion of the large roughness is smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is smaller than the depth of a concave portion thereof.
13. A method for manufacturing an ice and snow accretion-preventive antenna, electric wire, and insulator comprising:
processing a surface of a base material itself by blasting or dimpling to form large roughness having a size in the range of 500 to 10 μm on the surface,
performing chemical etching or electrolytic etching on the surface of the base material itself to form small roughness having a size of less than 10 μm and 10 nm or more on the surface, and
forming a water-repellent, oil-repellent, and antifouling monomolecular film covering the large roughness and the small roughness and containing —CF3 group,
wherein the area of a convex portion of the large roughness is smaller than the area of a concave portion thereof, and the interval between convex portions of the small roughness is smaller than the depth of a concave portion thereof
US12/600,144 2007-05-14 2008-05-13 Ice and snow accretion-preventive antenna, electric wire, and insulator having water-repellent, oil-repellent, and antifouling surface and method for manufacturing the same Expired - Fee Related US8872709B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2007127572A JP2008282750A (en) 2007-05-14 2007-05-14 Ice-accretion and snow-accretion preventive antenna and electric wire, insulator having water-repellent and oil-repellent anti-fouling surfaces, and their manufacturing method
JP2007-127572 2007-05-14
PCT/JP2008/058780 WO2008143065A1 (en) 2007-05-14 2008-05-13 Icing and snow accretion preventive antenna, electric wire and insulator having water repellent, oil repellent and anti-fouling surface, and method for manufaturing the same

Publications (2)

Publication Number Publication Date
US20100220018A1 true US20100220018A1 (en) 2010-09-02
US8872709B2 US8872709B2 (en) 2014-10-28

Family

ID=40031774

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/600,144 Expired - Fee Related US8872709B2 (en) 2007-05-14 2008-05-13 Ice and snow accretion-preventive antenna, electric wire, and insulator having water-repellent, oil-repellent, and antifouling surface and method for manufacturing the same

Country Status (3)

Country Link
US (1) US8872709B2 (en)
JP (1) JP2008282750A (en)
WO (1) WO2008143065A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013156349A1 (en) 2012-04-19 2013-10-24 Florian Felix Anti-adhesion coating against snow and ice
CN105989924A (en) * 2015-02-11 2016-10-05 国家电网公司 Bare conductor possessing super hydrophobicity
CN105989923A (en) * 2015-02-11 2016-10-05 国家电网公司 Anti-icing high voltage wire
CN106356164A (en) * 2016-11-14 2017-01-25 广东电网有限责任公司电力科学研究院 Surface treatment technology for anti-icing composite insulator
WO2018001889A1 (en) 2016-06-28 2018-01-04 Evonik Degussa Gmbh Composition based on polysiloxanes

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5306255B2 (en) * 2010-02-17 2013-10-02 三菱電機株式会社 Antenna radiating element and planar antenna provided with the same
WO2021090812A1 (en) * 2019-11-05 2021-05-14 ダイキン工業株式会社 Antenna cover base material

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210687A (en) * 1977-09-07 1980-07-01 Chemische Werke Huls Aktiengesellschaft Method for the coating of glass surfaces
US5324566A (en) * 1991-01-23 1994-06-28 Matsushita Electric Industrial Co., Ltd. Water and oil repelling film having surface irregularities and method of manufacturing the same
WO1998042452A1 (en) * 1997-03-20 1998-10-01 Unisearch Limited Hydrophobic films
WO2001014497A1 (en) * 1999-08-20 2001-03-01 Unisearch Limited Hydrophobic material
US20010005531A1 (en) * 1995-06-14 2001-06-28 Kazufumi Ogawa Method for manufacturing a chemically adsorbed film and a chemical adsorbent solution for the method
US20010051273A1 (en) * 1999-05-03 2001-12-13 Guardian Industries Hydrophobic coating including DLC on substrate
US6337129B1 (en) * 1997-06-02 2002-01-08 Toto Ltd. Antifouling member and antifouling coating composition
US20020045010A1 (en) * 2000-06-14 2002-04-18 The Procter & Gamble Company Coating compositions for modifying hard surfaces
US20020192385A1 (en) * 2001-01-05 2002-12-19 Degussa Ag Method of applying a fluoroalkyl-functional organopolysiloxane coationg having durable water and oil repellent properties to polymeric substrates
WO2004090065A1 (en) * 2003-04-11 2004-10-21 Unisearch Limited Durable superhydrophobic coating
EP1479738A1 (en) * 2003-05-20 2004-11-24 DSM IP Assets B.V. Hydrophobic coatings comprising reactive nano-particles
WO2005021843A1 (en) * 2003-09-02 2005-03-10 Sabanci Universitesi Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them
US20050136180A1 (en) * 2003-12-19 2005-06-23 3M Innovative Properties Company Method of coating a substrate with a fluoropolymer
WO2005068400A1 (en) * 2004-01-15 2005-07-28 Newsouth Innovations Pty Limited Hydrophobic coating composition
EP1640419A1 (en) * 2004-09-28 2006-03-29 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Water repellent coating comprising a hydrophobically modified layered silicate
US20060154048A1 (en) * 2002-12-10 2006-07-13 Toyoyuki Teranishi Article having functional coating film thereon, method for manufacture thereof, and applying material for forming functional coating film
US7635522B2 (en) * 2003-02-28 2009-12-22 Koninklijke Philips Electronics N.V. Fluoropolymer-containing sol-gel coating
US20100119774A1 (en) * 2007-03-30 2010-05-13 Kazufumi Ogawa Water-repellent, oil-repellent, and antifouling antireflection film and method for manufacturing the same, lens, glass sheet, and glass coated with the same, and optical apparatus, solar energy system, and display equipped with these components
US20100167067A1 (en) * 2008-12-31 2010-07-01 Hung Chi-Hsiang Coating structure, chemical composition for forming the same, and method of forming the same
US20100212736A1 (en) * 2007-12-12 2010-08-26 Kazufumi Ogawa Solar energy utilization device and method for manufacturing the same
US20100330373A1 (en) * 2007-05-01 2010-12-30 Kazufumi Ogawa Water repellent glass plates
US7959826B2 (en) * 2004-08-16 2011-06-14 Honeywell International Inc. Methods of preventing frost formation and facilitating the removal of winter precipitation relative to a windshield and compositions for use therein
US7985475B2 (en) * 2003-04-28 2011-07-26 Nanosys, Inc. Super-hydrophobic surfaces, methods of their construction and uses therefor

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02258032A (en) 1989-03-30 1990-10-18 Asahi Chem Ind Co Ltd Desalting method
JPH08195126A (en) * 1995-01-18 1996-07-30 Mitsui Eng & Shipbuild Co Ltd Ice/snow sticking prevention type power transmission line
JPH11171592A (en) 1997-12-15 1999-06-29 Nippon Sheet Glass Co Ltd Water-repellent article and its manufacture
JP2006067834A (en) 2004-08-31 2006-03-16 Daiwa Seiko Inc Surface treatment agent for fishing tackle
JP2006181486A (en) 2004-12-27 2006-07-13 Hokkaido Univ Method for forming fine ruggedness structure and its utilization

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210687A (en) * 1977-09-07 1980-07-01 Chemische Werke Huls Aktiengesellschaft Method for the coating of glass surfaces
US5324566A (en) * 1991-01-23 1994-06-28 Matsushita Electric Industrial Co., Ltd. Water and oil repelling film having surface irregularities and method of manufacturing the same
US5437894A (en) * 1991-01-23 1995-08-01 Matsushita Electric Industrial Co., Ltd. Method of manufacturing a water- and oil-repelling film having surface irregularities
US20010005531A1 (en) * 1995-06-14 2001-06-28 Kazufumi Ogawa Method for manufacturing a chemically adsorbed film and a chemical adsorbent solution for the method
WO1998042452A1 (en) * 1997-03-20 1998-10-01 Unisearch Limited Hydrophobic films
US6337129B1 (en) * 1997-06-02 2002-01-08 Toto Ltd. Antifouling member and antifouling coating composition
US20010051273A1 (en) * 1999-05-03 2001-12-13 Guardian Industries Hydrophobic coating including DLC on substrate
WO2001014497A1 (en) * 1999-08-20 2001-03-01 Unisearch Limited Hydrophobic material
US20020045010A1 (en) * 2000-06-14 2002-04-18 The Procter & Gamble Company Coating compositions for modifying hard surfaces
US20020192385A1 (en) * 2001-01-05 2002-12-19 Degussa Ag Method of applying a fluoroalkyl-functional organopolysiloxane coationg having durable water and oil repellent properties to polymeric substrates
US20060154048A1 (en) * 2002-12-10 2006-07-13 Toyoyuki Teranishi Article having functional coating film thereon, method for manufacture thereof, and applying material for forming functional coating film
US7635522B2 (en) * 2003-02-28 2009-12-22 Koninklijke Philips Electronics N.V. Fluoropolymer-containing sol-gel coating
WO2004090065A1 (en) * 2003-04-11 2004-10-21 Unisearch Limited Durable superhydrophobic coating
US7985475B2 (en) * 2003-04-28 2011-07-26 Nanosys, Inc. Super-hydrophobic surfaces, methods of their construction and uses therefor
EP1479738A1 (en) * 2003-05-20 2004-11-24 DSM IP Assets B.V. Hydrophobic coatings comprising reactive nano-particles
WO2005021843A1 (en) * 2003-09-02 2005-03-10 Sabanci Universitesi Process for preparing superhydrophobic surface compositions, surfaces obtained by said process and use of them
US20050136180A1 (en) * 2003-12-19 2005-06-23 3M Innovative Properties Company Method of coating a substrate with a fluoropolymer
WO2005068400A1 (en) * 2004-01-15 2005-07-28 Newsouth Innovations Pty Limited Hydrophobic coating composition
US7959826B2 (en) * 2004-08-16 2011-06-14 Honeywell International Inc. Methods of preventing frost formation and facilitating the removal of winter precipitation relative to a windshield and compositions for use therein
EP1640419A1 (en) * 2004-09-28 2006-03-29 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Water repellent coating comprising a hydrophobically modified layered silicate
US20100119774A1 (en) * 2007-03-30 2010-05-13 Kazufumi Ogawa Water-repellent, oil-repellent, and antifouling antireflection film and method for manufacturing the same, lens, glass sheet, and glass coated with the same, and optical apparatus, solar energy system, and display equipped with these components
US20100330373A1 (en) * 2007-05-01 2010-12-30 Kazufumi Ogawa Water repellent glass plates
US20100212736A1 (en) * 2007-12-12 2010-08-26 Kazufumi Ogawa Solar energy utilization device and method for manufacturing the same
US20100167067A1 (en) * 2008-12-31 2010-07-01 Hung Chi-Hsiang Coating structure, chemical composition for forming the same, and method of forming the same
US20120027995A1 (en) * 2008-12-31 2012-02-02 Hung Chi-Hsiang Coating structure, chemical composition for forming the same, and method of forming the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Yavuz Yuce, M., A. Levent Demirel and Frank Menzel. "Tuning the Surface Hydrophobicity of Polymer/Nanoparticle Composite Films in the Wenzel Regime by Componsition, American Chemical Society, April 21, 2005. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013156349A1 (en) 2012-04-19 2013-10-24 Florian Felix Anti-adhesion coating against snow and ice
DE102012007829A1 (en) 2012-04-19 2013-10-24 Florian Felix Anti-adhesion coating against snow and ice
CN105989924A (en) * 2015-02-11 2016-10-05 国家电网公司 Bare conductor possessing super hydrophobicity
CN105989923A (en) * 2015-02-11 2016-10-05 国家电网公司 Anti-icing high voltage wire
WO2018001889A1 (en) 2016-06-28 2018-01-04 Evonik Degussa Gmbh Composition based on polysiloxanes
CN106356164A (en) * 2016-11-14 2017-01-25 广东电网有限责任公司电力科学研究院 Surface treatment technology for anti-icing composite insulator

Also Published As

Publication number Publication date
WO2008143065A1 (en) 2008-11-27
JP2008282750A (en) 2008-11-20
US8872709B2 (en) 2014-10-28

Similar Documents

Publication Publication Date Title
US8872709B2 (en) Ice and snow accretion-preventive antenna, electric wire, and insulator having water-repellent, oil-repellent, and antifouling surface and method for manufacturing the same
US9160053B2 (en) Icing and snow accretion preventive insulator, electric wire, and antenna, method for manufacturing them, and transmission line tower using them
EP2463348B1 (en) Composition for formation of water-repellent film, base material having water-repellent film attached thereto and process for production thereof, and article for transport device
KR100902529B1 (en) Dispersion of titanium oxide particles, titanium oxide thin film, solution for forming organic functional film, substrate having organic functional film formed thereon and method for producing same
JP4670057B2 (en) Method for producing water and oil repellent antifouling glass plate
US20100119774A1 (en) Water-repellent, oil-repellent, and antifouling antireflection film and method for manufacturing the same, lens, glass sheet, and glass coated with the same, and optical apparatus, solar energy system, and display equipped with these components
JP2007118276A (en) Single-layer fine particle film, cumulated fine particle film and manufacturing method of them
WO2008068873A1 (en) Monolayer nanoparticle film, multilayer nanoparticle film, and manufacturing method thereof
JP5050190B2 (en) Fine particles and production method thereof
US9330807B2 (en) Conductive paste and method for manufacturing the same, wiring using the conductive paste and method for manufacturing the same
JP5487460B2 (en) Silicon fine particles, production method thereof, solar cell using the same, and production method thereof
JP2008137858A (en) Water repellent, oil repellent antifouling glass plate, its manufacturing method and automobile using the glass plate
JP2012046765A (en) Solution for preparing water repellent and oil repellent antifouling composite film, method for preparing water repellent and oil repellent antifouling composite film by using the same, and water repellent and oil repellent antifouling composite film by using the same
JP5422855B2 (en) Transfer roll, method for producing the same, and film or sheet produced using the same
JP5326086B2 (en) Solar energy utilization apparatus and manufacturing method thereof
JP2008279398A (en) Member having water-repellent and oil-repellent antifouling property surface, and manufacturing method of the water-repellent and oil-repellent antifouling property surface
He et al. Synthesis and characterization of cathodic electrodeposition coatings based on octadecyl-modified cationic waterborne polyurethanes
US9174366B2 (en) Metal mold, process for manufacturing the same, and molded article produced using the mold
WO2017159867A1 (en) Coating
WO2015137344A1 (en) Composite material of resin-fluorine-containing boric acid composite particles
US8658888B2 (en) Solar energy utilization device and method for manufacturing the same
KR20110033332A (en) Antenna, cable and insulator preventing icing and frosted
JP2017132927A (en) Hydrophilic oil repellent recovery agent, recovery method of hydrophilic oil repellency of hydrophilic oil repellent coated film and hydrophilic oil repellent coated film
WO2010023714A1 (en) Mold and process for producing the mold
WO2009104236A1 (en) Water repellent, oil repellent antifouling glass plate, process for producing the same and automobile utilizing the glass plate

Legal Events

Date Code Title Description
AS Assignment

Owner name: EMPIRE TECHNOLOGY DEVELOPMENT LLC, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OGAWA, KAZUFUMI;REEL/FRAME:030803/0258

Effective date: 20130517

AS Assignment

Owner name: EMPIRE TECHNOLOGY DEVELOPMENT LLC, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OGAWA, KAZUFUMI;REEL/FRAME:030848/0459

Effective date: 20130517

STCF Information on status: patent grant

Free format text: PATENTED CASE

CC Certificate of correction
MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551)

Year of fee payment: 4

AS Assignment

Owner name: CRESTLINE DIRECT FINANCE, L.P., TEXAS

Free format text: SECURITY INTEREST;ASSIGNOR:EMPIRE TECHNOLOGY DEVELOPMENT LLC;REEL/FRAME:048373/0217

Effective date: 20181228

AS Assignment

Owner name: EMPIRE TECHNOLOGY DEVELOPMENT LLC, WASHINGTON

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CRESTLINE DIRECT FINANCE, L.P.;REEL/FRAME:049924/0794

Effective date: 20190501

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20221028